EP3029122B1 - Sheet composed of exfoliated clay mineral and method for producing same - Google Patents

Sheet composed of exfoliated clay mineral and method for producing same Download PDF

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Publication number
EP3029122B1
EP3029122B1 EP14831589.8A EP14831589A EP3029122B1 EP 3029122 B1 EP3029122 B1 EP 3029122B1 EP 14831589 A EP14831589 A EP 14831589A EP 3029122 B1 EP3029122 B1 EP 3029122B1
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EP
European Patent Office
Prior art keywords
sheet
clay minerals
exfoliated
sealing material
montmorillonite
Prior art date
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EP14831589.8A
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German (de)
English (en)
French (fr)
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EP3029122A4 (en
EP3029122A1 (en
Inventor
Hirotaka NATORI
Tomokazu Watanabe
Nahoko KITAJIMA
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Nichias Corp
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Nichias Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1003—Pure inorganic mixtures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J15/00—Sealings
    • F16J15/02—Sealings between relatively-stationary surfaces
    • F16J15/06—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
    • F16J15/102—Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing characterised by material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1034—Materials or components characterised by specific properties
    • C09K2003/1078—Fire-resistant, heat-resistant materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2003/1084—Laminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0252—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0243—Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0265—Mica

Definitions

  • the invention relates to a sheet suitable for use as a sealing material and a method for producing the same.
  • a sealing material such as a gasket and a packing is used in a pipe flange or the like in various industries.
  • a sealing material is required to have the properties mentioned below. Since pipes are frequently exposed to high temperatures, it is required to have heat resistance sealing properties. Further, since a sealing material is cut off from a sheet at the time of production, it is required to have a strength enough to resist punching with a Thomson blade. Further, a sealing material is required to have a large compression amount in order to be in imitate contact with a flange having concave and convex on the surface thereof.
  • a sealing material made of expanded graphite is known (for example, see JP-A-2011-046794 , JP-A-H10-130626 , JP-A-2013-052680 , JP 3310619 ).
  • a sealing material made of expanded graphite has sufficient elasticity and is excellent in heat resistance.
  • disappearance by oxidation of expanded graphite is accelerated in the presence of oxygen in a temperature range exceeding 500°C, it is difficult to maintain stable sealing properties for a long period of time.
  • JP-A-H06-249345 , JP 5047490 , and JP-A-S60-155523 disclose a sealing material made of mica.
  • the sealing material disclosed in JP-A-H06-249345 is a composite material (vortex) of swelling mica and fibers. Due to the use of fibers, it has poor sealing properties. Further, since it is prepared by papermaking, mica that is exfoliated is re-aggregated during drying, and thus only a dense thin film is formed, leading to a small compression amount.
  • the sealing material disclosed in JP 5047490 is a sheet (vortex) of swelling mica. Since only a high dense sheet can be produced, the sheet has a small compression amount.
  • the sealing material disclosed in JP-A-S60-155523 is a film of swelling mica, and has a small compression amount.
  • JP 3855003 , JP-A-2011-001231 , and JP-A-2012-193750 each disclose a sealing material using clay.
  • a sealing material using clay.
  • the sealing material in JP-A-2011-001231 is a composite material of clay and fibers. As for this composite material, flexibility is imparted by fibers. However, this composite material had poor sealing properties.
  • WO 80/01576 A1 and US 4 271 228 A disclose a flexible sheet material, e.g.
  • FR 2 882 997 discloses a process for exfoliating an intercalated clay.
  • WO 2005/068365 A1 discloses a method for the preparation of exfoliated nanoclays from ordinary layered smectic clays.
  • An object of the invention is to provide a sheet that is excellent in heat resistance, has a large compression amount and is excellent in handling properties, and a sealing material.
  • the present invention concerns a sheet comprising exfoliated clay minerals, having a density of 1.6 g/cm 3 or less and a compression ratio of 20% or more, wherein the clay minerals are selected from the following group: mica, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite or nontronite, and the sheet comprises 90 wt% or more of the exfoliated clay minerals.
  • the clay minerals preferably are natural clay or synthetic clay.
  • the natural clay or the synthetic clay is mica, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite or nontronite.
  • the exfoliated clay minerals preferably have a thickness of 0.5 nm to 1000 nm.
  • the exfoliated clay minerals preferably are a single layer or a laminate of two or more layers.
  • a void ratio of voids has a major axis of 15 ⁇ m or more is 3 vol% or less.
  • the sealing properties are lowered by 5 times or less after a heat cycle test of 450°C or more in the air.
  • a sheet according to another preferred embodiment has a bending strength of 1 MPa or more.
  • the invention further concerns a sealing material obtained by using the sheet according to one of the above mentioned embodiments.
  • the sealing material is a gasket or a packing.
  • the invention further concerns a method for producing a sheet according to one of the above mentioned embodiments, comprising:
  • the exfoliated clay minerals are formed into a sheet by assembling them without allowing them to be oriented.
  • the bulk density of the exfoliated clay minerals is 0.4g/cm 3 or less.
  • the invention it is possible to provide a sheet that is excellent in heat resistance, has a large compression amount and excellent handling properties, and a sealing material.
  • the sheet according to the invention is formed of exfoliated clay minerals (clay mineral thin strips) that are assembled without being oriented, and hence it has fine voids inside. Therefore, the sheet has a large compression amount, and as a result, is capable of absorbing (removing or filling) concave and convex or distortion on a flange surface. Accordingly, it can be used as a sealing material. In particular, it is preferably used as a sealing material for a flange.
  • a ring-like sealing material 10 is disposed between flanges 3 of a pipe1, and fixed by means of a bolt 7 and a nut 5.
  • a gas or a liquid is flown in the direction of an arrow.
  • the sealing material 10 is required to have a compression amount that is enough to absorb convex and concave on the contact surface of the flange 3.
  • leakage in the plane direction is divided into substantial leakage (i.e. leakage through a sealing material itself) and leakage along a contact surface.
  • the substantial leakage is leakage that a gas or a liquid passes through the sealing material.
  • Leakage along a contact surface is leakage from a gap between the sealing material and the flange.
  • Such leakage along a contact surface occurs for the following reasons: concave and convex on the flange surface that are formed when processing a flange; a gap formed on the contact surface between a flange and a sealing material due to deformation generated when the flange is tightened by a bolt; and thermal deformation of a flange caused by heating or cooling.
  • the sealing material of the invention has a large compression amount, as shown in Fig. 2(b) , when tightened by a bolt, it conforms to the concave and convex, or the deformation on the flange surface, whereby leakage along the contact surface can be prevented.
  • exfoliated clay minerals are not oriented and arranged irregularly. Therefore, fine voids are present inside the sealing material. Therefore, a compression amount is large, whereby it is possible to absorb concave and convex on the flange surface. As a result, when used in a flange having concave and convex on the surface, the quantity of leakage from contact surface is small.
  • Fig. 3(b) if exfoliated clay minerals are oriented, only a small amount of gaps are present in the inside, and the amount of compression is small. Therefore, this sealing material cannot absorb concave and convex on the flange surface due to a small compression amount, and hence, when used in a flange having concave and convex on the surface, a large quantity of leakage occurs.
  • Exfoliated clay minerals constituting the sheet of the invention normally has a thickness of 0.5 nm to 1000 nm. These exfoliated clay minerals can be obtained by various methods.
  • clay minerals natural clay minerals or synthetic clay minerals may be used.
  • the clay minerals are selected from the following group:, mica, montmorillonite, iron montmorillonite, beidellite, saponite, hectorite, stevensite or nontronite can be exemplified. These clay minerals are laminar compounds in which thin strips are laminated in the form of a layer.
  • exfoliated clay minerals exfoliated strips obtained by exfoliating clay mineral can be used. It is preferred that this exfoliated strip be made of a single layer.
  • the exfoliated strip may be a laminate of a plurality of layers.
  • the degree of exfoliation relates to the thickness of a laminate or the bulk density of a laminate.
  • the exfoliated strips obtained by exfoliating clay mineral used when preparing the sheet of the invention have preferably a smaller bulk density, since a smaller bulk density leads to a large compression amount.
  • the bulk density is preferably 0.4 g/cm 3 or less. Within this range, a sheet realizing an appropriate compression amount and having a bending strength that can withstand punching processing is obtained.
  • the bulk density is preferably 0.2 g/cm 3 or less, more preferably 0.1 g/cm 3 or less.
  • the density of the sheet of the invention is 1.6 g/cm 3 or less, more preferably 1.5 g/cm 3 or less, further preferably 1.4 g/cm 3 or less, with 1.1 g/cm 3 or less being most preferable.
  • the compression ratio of the sheet of the invention is 20% or more when measured by the method described in the Examples.
  • the upper limit is not particularly restricted, but normally 90% or less. If the compression ratio is large, it is possible to maintain the intimate contact between the sheet and the flange.
  • the compression ratio is more preferably 23% or more, and further preferably 25% or more.
  • lowering in sealing properties (heat resistance) after heat cycles (3 times) of 450°C or more in the air when measurement is conducted by the method described in the Examples is preferably 5 times or less, more preferably 2 times or less.
  • the bending strength is 1 MPa or more, more preferably 1.5 MPa or more. If the bending strength is high, the sheet can sufficiently withstand punching or the like.
  • the upper limit is not restricted, but normally 25 MPa or less.
  • the void ratio as referred to herein means the ratio of the total sum of the volumes of voids having a major axis of 15 ⁇ m or more to the sheet volume. In view of strength, when measured by the method described in the Examples, it is preferred that the void ratio of voids having a major axis of 15 ⁇ m or more be 3 vol% or less, more preferably 1.5 vol% or less.
  • the quantity of leakage in the plane direction at a surface fastening pressure of 34 MPa is preferably 0.4 atmcc/min or less, more preferably 0.35 atmcc/min or less, and further preferably 0.2 atmcc/min or less.
  • the sheet of the invention may contain a binder or the like.
  • the sheet of the invention may be composed of 90 wt% or more, 95 wt% or more, 98 wt% or more or 100 wt% of exfoliated clay minerals.
  • the sheet of the invention can be produced by assembling and forming into a sheet exfoliated clay minerals without allowing them to be oriented.
  • the method for producing the exfoliated clay minerals is not restricted.
  • Clay minerals are exfoliated, and a dispersion in which exfoliated clay minerals are dispersed is frozen, and the frozen dispersion is freeze-dried, followed by compression molding.
  • a dispersion in which exfoliated clay minerals are dispersed is frozen, and the frozen dispersion is freeze-dried, followed by compression molding.
  • swelling mica is used as clay mineral
  • the swelling mica is swollen when put in water.
  • layers constituting mica are exfoliated, whereby a dispersion can be obtained.
  • water is removed by drying while keeping the dispersed state, and as a result, exfoliated strips of mica are obtained in a state where the exfoliated strips are irregularly dispersed.
  • the exfoliated strips of mica are put in a mold, and then is subjected to compression molding to an appropriate thickness, whereby a sheet having an appropriate density and an appropriate size can be obtained.
  • the thickness of the resulting sheet is normally about 0.1 to 10 mm.
  • the sheet of the invention can be used as a sealing material (e.g. gasket, packing) of various pipes in various industries such as exhaust pipes of an automobile.
  • the sheet can be used as a sealing material itself.
  • the sheet can be used as part of a sealing material.
  • the sheets of the invention are attached, as an outer layer, to the both surfaces of a member (metal main body) having concave and convex (groove, etc.) on the both surfaces thereof, and the resultant can be used as a gasket.
  • the outer layers enter the concave and convex, and as a result, not only damage to the flange can be suppressed, but also sealing properties are improved.
  • the frozen clay was then freeze-dried by means of a freeze drier "FDU-2110" (manufactured by Tokyo Rika Kikai Co., Ltd.), whereby exfoliated strips of montmorillonite (montmorillonite nanosheet) (exfoliated clay materials) were obtained.
  • FDU-2110 manufactured by Tokyo Rika Kikai Co., Ltd.
  • the bulk density was measured by using an electronic balance "MC-1000" (manufactured by A&D Company, Ltd.) at room temperature of 23°C.
  • MC-1000 manufactured by A&D Company, Ltd.
  • the weight of a metal cylindrical container having an inner diameter of 20 mm (volume: 25 cm 3 ) was measured.
  • an excessive amount of the exfoliate strips was put, and part of the exfoliated strips that was overflown from the container was levelled off by a metal plate.
  • 0.844g of the exfoliated strips of the montmorillonite was put in a mold (having a cylindrical recess with a diameter of 34 mm and a depth of 1 mm), and was subjected to compression molding with a flat and smooth metal plate such that the thickness became 1 mm.
  • the density and thickness of the sheet were 0.93 g/cm 3 and 1 mm, respectively.
  • FIG. 4 A scanning electron micrograph of the cross section of the obtained sheet is shown in FIG. 4 . It can be understood that the exfoliated strips (montmorillonite nanosheet) were assembled irregularly without being oriented.
  • the montmorillonite sheet was a single layer or a laminate.
  • the thickness was found to be 10 to 800 nm.
  • Exfoliated strips of montmorillonite were obtained in the same manner as in Example 1, except that 30g of "Kunipia M” (manufactured by Kunimine Industries, Co., Ltd.) as natural montmorillonite was added to 70g of distilled water.
  • a sheet was prepared in the same manner as in Example 1 by using 0.853g of the exfoliated strips of montmorillonite.
  • Exfoliated strips of vermiculite were obtained in the same manner as in Example 1, except that, as clay, one obtained by pulverizing chemically-treated vermiculite "Micro Light Powder (registered trademark)" (manufactured by Specialty Vermiculite Corporation) in a mortar such that the median diameter D50 became 4 ⁇ m was used.
  • a sheet was prepared in the same manner as in Example 1 by using 0.898g of the exfoliated strips of vermiculate.
  • Exfoliated strips of mica were obtained in the same manner as in Example 1, except that, as clay, swelling mica "DMA-350” that was sodium tetrasilicate mica (manufactured by Topy Industries Limited.) was used.
  • a sheet was prepared in the same manner as in Example 1 by using 0.889g of this exfoliated strips.
  • a sheet was prepared in the same manner as in Example 1, except that 1.27g of the exfoliated strips of mica obtained in Example 4 was used.
  • Exfoliated strips were obtained in the same manner as in Example 1, except that, as clay, 30g of swelling mica "DMA-350” that was sodium tetrasilicate mica (manufactured by Topy Industries Limited.) was used. By using 0.453g of these exfoliated strips of mica, a sheet was prepared in the same manner as in Example 1.
  • Example 4 By using 1.54g of the exfoliated strips of mica obtained in Example 4, a sheet was prepared in the same manner as in Example 1.
  • Example 1 of Patent Document 8 a sheet of montmorillonite was prepared. Specifically, a dispersion of clay obtained in Example 1 above was poured to a tray, and the clay dispersion was allowed to stand horizontally to cause clay particles to deposit slowly. While keeping the horizontal state of the tray, drying was conducted in a forced-air oven at 50°C for 5 hours, whereby a sheet having a thickness of about 40 ⁇ m was obtained. A scanning electron microscope of the cross section of the resulting sheet is shown in Fig. 5 . It can be understood that montmorillonite nanosheets were oriented.
  • a compression ratio means a value obtained from a ratio of a deformation amount when the sheet was compressed under 34 MPa (corresponding to a surface pressure that is normally applied to a gasket of a pipe or the like) to the initial thickness.
  • the compression ratio of a sheet sample was measured by means of a universal material testing machine "AG-100kN" (manufactured by Shimadzu Corporation).
  • AG-100kN manufactured by Shimadzu Corporation.
  • a metal cylindrical plate having a diameter of 15 mm and a thickness of 2 mm was compressed at a speed of 0.1 mm/min, and distortion when compressed under 34 MPa was measured in advance.
  • the bending strength of the sheet sample was measured by means of a dynamic viscoelasticity spectrometer "RSAIII" (manufactured by TA Instruments Japan, Inc.).
  • the sample used for the measurement had a width of 10 mm, a length of 20 mm and a thickness of 1 mm.
  • the measurement was conducted by the 3-point bending test under the condition of an inter-fulctrum distance of 10 mm and a testing speed of 1 mm/min.
  • the void ratio of the sample was measured by means of an X-ray CT apparatus "SKYSCAN1072" (manufactured by Bruker-microCT Co., Ltd.).
  • the sample for the measurement was carefully cut by means of a laser blade such that it became a cube having a length of one side of 1 to 2 mm and no cracks were caused by the cutting.
  • the sample was rotated for an exposure time of 1.1 second, 2 frames and a rotation step of 0.23° from 0 to 180°, and a transmitted image was acquired. Not only the sample but also a space around the sample was photographed. A line profile of the transmitted image was confirmed, and the gain was adjusted such that a difference was observed between the sample part and the space part.
  • This gray value was segmented as the threshold value of the void, and the volume of each void was measured by the Marching Cubes method.
  • the gas transmission coefficient in the thickness direction was measured according to the differential pressure method (JIS K7126-1) by means of a differential gas permeability tester "GTR-30ANI" (manufactured by GTR Tec Corporation). A sample used for the measurement was obtained by cutting a sheet having a thickness of 0.5 mm by means of a cutter knife such that the diameter became 58 mm.
  • the measurement conditions of the gas permeability coefficient were as follows. Sample temperature was 30°C; measurement cell had a transmission cross section of 15.2 cm 2 ; helium gas was pressurized under 0.049 MPa; and differential pressure was 0.149 MPa. The quantity of a helium gas that had transmitted at a differential pressure of 0.149 MPa for an arbitrary period of time was measured. The permeability coefficient was calculated by the following formula. All of the tests were conducted in a room at a temperature of 23 ⁇ 0.5°C.
  • GTR Q ⁇ T A ⁇ t ⁇ ⁇ P
  • a ring (outer diameter: 30 mm, inner diameter: 15 mm) obtained by punching the resulting sheet by means of a Thomson blade was placed on a flange (made of SUS-F304 25A).
  • the flange was fastened by 4 bolts (made of SUS-F304, M16) under 34 MPa.
  • the initial leakage quantity when a nitrogen gas was applied under 1 MPa was measured by the same pressure drop method as that used for measuring the quantity of leakage in the plane direction in (d) of Evaluation Example 1.
  • This flange was placed in a thermo-hygrostat (Super High-Temp Oven SSP H-101) (manufactured by Espec Corp.).
  • the temperature was elevated in the air from 40°C to 600°C at a temperature elevation rate of 5°C/min, and kept at 600°C for 17 hours. Then, the temperature was lowered to 40°C at a temperature lowering rate of 5°C/min. After holding the flange in a room of 23°C ⁇ 0.5°C for 6 hours, the quantity of leakage was measured. A change from the initial quantity of leakage was evaluated. This heating operation was repeated three times, and a change from the initial quantity of leakage was calculated. Table 1 Ex. 1 Ex. 2 Ref. Ex. 1 Ex. 4 Ex. 5 Ex. 6 Comp. Ex. 1 Comp. Ex.
  • the sheet of the present invention can be used in sealing materials such as a gasket, a packing or the like for various pipes in various industries, e.g., exhaust pipes of an automobile.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Sealing Material Composition (AREA)
  • Gasket Seals (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
EP14831589.8A 2013-08-01 2014-07-16 Sheet composed of exfoliated clay mineral and method for producing same Active EP3029122B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013160162 2013-08-01
PCT/JP2014/003771 WO2015015737A1 (ja) 2013-08-01 2014-07-16 薄片状粘土鉱物からなるシート及びその製造方法

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EP3029122A1 EP3029122A1 (en) 2016-06-08
EP3029122A4 EP3029122A4 (en) 2017-05-10
EP3029122B1 true EP3029122B1 (en) 2021-10-13

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US (1) US10563104B2 (ja)
EP (1) EP3029122B1 (ja)
JP (1) JP6433426B2 (ja)
CN (1) CN105531341B (ja)
WO (1) WO2015015737A1 (ja)

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Publication number Priority date Publication date Assignee Title
US10544864B2 (en) 2015-02-02 2020-01-28 Nichias Corporation Gasket and manufacturing method thereof
JP6992245B2 (ja) * 2016-03-31 2022-01-13 日本ケミコン株式会社 無機化合物の製造方法、封止材の製造方法、および封止材
US9643889B1 (en) * 2016-04-08 2017-05-09 King Saud University Method of storing exfoliated nanoclay particles
JP6957241B2 (ja) * 2017-07-03 2021-11-02 日本ケミコン株式会社 無機化合物の製造方法および封止材の製造方法
CN107583601B (zh) * 2017-09-20 2020-01-31 武汉理工大学 一种层状硅酸盐矿物材料高效吸附剂的制备方法
CN107722515B (zh) * 2017-10-30 2020-01-24 杨云 一种高温蛭石密封材料的制备方法与装置
CN114620739B (zh) * 2022-03-30 2023-08-25 浙江省地质院 一种纳米片层叶蜡石粉体及其制备方法

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CN105531341A (zh) 2016-04-27
CN105531341B (zh) 2018-03-16
US20160194536A1 (en) 2016-07-07
WO2015015737A1 (ja) 2015-02-05
US10563104B2 (en) 2020-02-18
JPWO2015015737A1 (ja) 2017-03-02
EP3029122A4 (en) 2017-05-10
EP3029122A1 (en) 2016-06-08

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